Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Homogeneous Catalysis (VI). Hydride Route with Chloro Ligand Dissociation for the Hydrogenation of Acrylonitrile with trans-Chlorocarbonylbis(triphenylphosphine)iridium(I)

  • Published : 1983.08.20
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Abstract

The reaction of $IrClH_2(CO)(Ph_3P)_2$ ($Ph_3P$=triphenylphosphine) with acrylonitrile (AN) produces a stoichiometric amount of propionitrile (PN) at $100^{\circ}C$ under nitrogen, which suggests that the catalytic hydrogenation of AN to PN with $IrCl(CO)(Ph_3P)_2$ proceeds through the hydride route where the formation of the dihydrido complex, $IrClH_2(CO)(Ph_3P)_2$ is the initial step. The rate of the hydrogenation of AN to PN with $IrCl(CO)(Ph_3P)_2$ is decreased by the presence of excess $Cl^-$ in the reaction system, which suggests that $Cl^-$ is the dissociating ligand in the catalytic cycle. It has been also found that the rate of the hydrogenation increases with inercase both in hydrogen pressure and in concentration of free $Ph_3P$, and with decrease in AN concentration in the reaction system.

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References

  1. J. Chem. Soc. v.A J.A. Osborn;F.H. Jardine;J.F. Young;G. Wilkinson
  2. J. Amer. Chem. Soc. v.94 P.Z. Meakin;J.P. Jesson;C.A. Tolman
  3. Chem. Commun. J. Halpern;C.S. Wong
  4. J. Amer. Chem. Soc. v.96 C.A. Tolman;P.Z. Meakin;D.L. Linder;J.P. Jesson
  5. Organotransition-Metal Chemistry J. Halpern;Y. Ishi(ed.);M. Tsutsui(ed.)
  6. J. Mol. Catalysis v.2 J. Halpern;T. Okamoto;A. Zakhariew
  7. Bull. Chem. Soc. Japan v.52 Y. Ohtani;A. Yamagishi;M. Fujimoto
  8. Z. Naturforsch. v.27b W. Stroheimer;Endes
  9. Chem. Commun. M.A. Bennett;D. L. Milner
  10. Z. Naturforsch. v.24b W. Stroheimer;W. Rehder-Stirnweiss
  11. Z. Naturforsch. v.26b W. Stroheimer;W. Rehder-Stirnweiss
  12. Z. Naturforsch. v.25b W. Rehder-Stirnweiss;R. Fleischmann
  13. J.C. Woo;C.S. Chin
  14. Homogeneous Catalysis G.W. Parshall
  15. Topics in Current Chemistry v.25 W. Stroheimer
  16. Can. J. Chem. v.46 B.R. James;N.A. Memon
  17. Z. Naturforsch. v.24b T. Onoda
  18. J. Organomet. Chem. v.29 R. Fleischmann
  19. J. Korean Chem. Soc. v.26 C.J. Moon;C.S. Chin
  20. Acc. Chem. Res. v.1 L. Vaska
  21. Inorg. Syntheses v.11 J.P. Collman;C.T. Sears, Jr.;M. Kubota
  22. J. Amer. Chem. Soc. v.87 L. Vaska;R.E. Rhodes